EP2782969B1 - Psa containing olefin block copolymers and styrene block copolymer - Google Patents

Psa containing olefin block copolymers and styrene block copolymer Download PDF

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Publication number
EP2782969B1
EP2782969B1 EP12790893.7A EP12790893A EP2782969B1 EP 2782969 B1 EP2782969 B1 EP 2782969B1 EP 12790893 A EP12790893 A EP 12790893A EP 2782969 B1 EP2782969 B1 EP 2782969B1
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EP
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Prior art keywords
hot
melt adhesive
block copolymers
adhesive
styrene block
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EP12790893.7A
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German (de)
French (fr)
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EP2782969A1 (en
Inventor
Eckhard Pürkner
Annie Seiler
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J147/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J193/00—Adhesives based on natural resins; Adhesives based on derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/387—Block-copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L93/00—Compositions of natural resins; Compositions of derivatives thereof

Definitions

  • the invention relates to hot-melt adhesives produced on the basis of olefin block copolymers and styrene block copolymers which, together with other additives, are suitable as pressure-sensitive hot-melt adhesives.
  • Hot melt adhesives that are suitable for bonding a wide variety of materials are generally known.
  • hot melt adhesives which are produced from an essentially linear copolymer of ethylene together with at least one C 3 to C 20 ⁇ -olefin monomer.
  • hot melt adhesives are manufactured based on linear ethylene- ⁇ -olefin copolymers.
  • the usual additional components are described there, for example tackifying resins, waxes, other different polymers, styrene block copolymers, plasticizers or other additives.
  • the purpose of use is the gluing of paper and cardboard materials, as well as use as adhesive tape or for bookbinding. Olefinic block copolymers are not described.
  • hot melt adhesives containing polyolefin polymers produced by metallocenes catalysis. These polymers are said to have a viscosity of up to 9000 mPas at a temperature of 149 ° C, the hot melt adhesive itself has a viscosity below 2000 mPas.
  • WO 2011/022523 A2 discloses a low application temperature hot melt adhesive based on olefin copolymers.
  • US 7199180 B1 discloses adhesives and processes for their preparation comprising at least a first homogeneous ethylene / ⁇ -olefin interpolymer and optionally, tackifiers and plasticizers.
  • JP 2009185122 A discloses propylene resin compositions excellent in mechanical strength properties and moldability.
  • Hot-melt adhesives can be produced from the known olefin copolymers.
  • the olefin copolymers can be varied within wide limits.
  • Styrene block copolymers are also widely available commercially. They can be produced with a wide range of properties, especially elastic polymers.
  • olefin copolymers are not sufficiently compatible with styrene block copolymers. In practice, this means that adhesives made from such mixtures are not storage-stable or when applied in the melt. The polymers can partially separate, in which case they cannot be applied or migrate to the surface and thus subsequently reduce the adhesion to the substrates. As a result, such mixtures are not suitable as permanently tacky pressure-sensitive hot melt adhesives.
  • the object of the present invention is therefore to provide hot-melt adhesives which consist of a mixture of olefin block copolymers and styrene block copolymers.
  • the hotmelt adhesives should have a suitable viscosity to enable application in thin layers and on temperature-sensitive substrates.
  • the layers obtained should show pressure-sensitively adhesive properties which are not impaired by storage of the adhesive.
  • the adhesive layers should show good elastic behavior in the bond.
  • a hot melt adhesive containing (i) 15 to 70% by weight of a mixture of at least one copolymer based on ethylene and / or propylene and at least one C4 to C20 ⁇ -olefin, which is polymerized by metallocenes as Block copolymer is obtainable and at least one styrene block copolymer, (ii) -10 to 70% by weight of at least one tackifying resin, (iii) 0 to 40% by weight of further additives and plasticizers, the sum of the percentages should be 100% and the tackifying resin is wholly or partly a soft resin which is liquid at a temperature below 50 ° C.
  • the invention also relates to the use of such hot-melt adhesives for coating films, tapes, labels and other flat substrates to produce a pressure-sensitive adhesive layer.
  • the invention furthermore relates to films, adhesive tapes and labels which have a pressure-sensitive adhesive layer of an adhesive according to the invention on at least one side.
  • a necessary component of the hot-melt pressure sensitive adhesive according to the invention are olefin copolymers based on ethylene and / or propylene and at least one C4 to C20 ⁇ -olefin. These polyolefins are produced using metallocene catalysis.
  • One embodiment of the invention uses such copolymers or terpolymers based on ethylene together with C4 to C20 ⁇ -olefins.
  • the monomers that can be used in addition to ethylene or propylene they are the known olefinically unsaturated monomers which can be copolymerized with ethylene or propylene.
  • ⁇ -olefins such as butene, hexene, methylpentene, octene; cyclically unsaturated compounds such as norbonene or norbonadiene; symmetrically or asymmetrically substituted ethylene derivatives, C1 to C12 alkyl radicals being suitable as substituents; and optionally unsaturated carboxylic acids or carboxylic acid anhydrides.
  • These can be homopolymers, copolymers, terpolymers, which can also contain further monomers. In the following, copolymers are also to be understood as meaning polymers composed of more than 2 monomers.
  • the amount of the ⁇ -olefin comonomers should preferably be below 20%.
  • Another embodiment contains copolymers based on ethylene and propylene. If necessary, it is possible that additional small proportions of C4 to C20 - ⁇ -olefins are also included. These are also produced using metallocenes catalysts.
  • the amount of propylene should be more than 60% by weight, in particular the proportion of propylene is more than 70% by weight. If necessary, small proportions of other ⁇ -olefin monomers may also be present, the amount should be less than 5%, but ethylene / propylene block copolymers are particularly suitable.
  • the (co) polymers obtained in this way have a molecular weight of 2,000 to 250,000 g / mol, in particular from 5,000 to 100,000 g / mol (molecular weight as number average, M N , determined via GPC). These (co) polymers are distinguished by the fact that they have a narrow molecular weight distribution.
  • the molecular weight distribution, expressed as M W / M N, should be, for example, up to 2.5, in particular below 2.3.
  • suitable polymers are commercially available under the trade name Vistamax® or Infuse®.
  • the copolymers suitable according to the invention are block copolymers.
  • the blocks have a different composition of the monomers.
  • the hot melt adhesives suitable according to the invention have one glass transition temperature, in another embodiment the copolymers should have two glass transition temperatures.
  • the first glass transition temperature (Tg) (measured via DTA) should be in the range between -100 to 0 ° C, in particular between -80 to -10 ° C.
  • the second glass transition temperature should in particular be below -100 ° C.
  • melt index of these polymers should be from 5 g / 10 min to 200 g / 10 min, preferably up to 100 g / 10 min (measured at 190 ° C., 2.16 kg, DIN ISO 1133).
  • the softening point of the polymers should be above 130.degree. C., in particular above 160.degree.
  • the amount of these copolymers should be 5 to 50% by weight based on the hot melt adhesive, in particular between 15 to 30% by weight.
  • the (co) polymers can be a polymer, but it is also possible that a mixture is used.
  • a hot melt pressure sensitive adhesive (PSA) according to the invention must contain at least one thermoplastic elastic styrene block copolymer. These are preferably triblock copolymers, but diblock copolymers can also be used, or mixtures of both types. Such block copolymers are poorly compatible with the olefin block copolymers.
  • styrene block copolymers There can be different types of styrene block copolymers. Examples of these are styrene-isoprene block copolymers (SIS), styrene-isoprene-butadiene block copolymers (SIBS), styrene-butadiene block copolymers (SBS), hydrogenated forms of the copolymers such as SBBS, SEBS, SEPS, SIPS or their mixtures, as well corresponding diblock copolymers.
  • SIS styrene-isoprene block copolymers
  • SIBS styrene-isoprene-butadiene block copolymers
  • SBS styrene-butadiene block copolymers
  • hydrogenated forms of the copolymers such as SBBS, SEBS, SEPS, SIPS or their mixtures, as well corresponding diblock copolymers.
  • M N molecular weight
  • the amount of styrene block copolymers contained in addition to the olefin block copolymers is from 3 to 35% by weight, in particular from 5 to 25% by weight, based on the hot-melt adhesive.
  • the elasticity of the adhesive is influenced by the amount of these block copolymers. If the amounts of block copolymers are too high, the adhesive is too elastic and difficult to process. In addition, incompatibilities are increasingly observed, which lead to poor adhesive properties. If the amount is too small, the cohesion of an adhesive layer is decreased.
  • the hot-melt pressure-sensitive adhesive according to the invention contains at least one tackifying resin as a further component.
  • the resin gives the adhesive additional tack. It is used in an amount of 10 to 70% by weight, preferably 10 to 40% by weight. According to the invention, it is necessary that the resins contain at least a proportion of a soft resin that is liquid or flowable below 50 ° C. This can be determined via the drop temperature.
  • Resins can be selected from aromatic, aliphatic or cycloaliphatic hydrocarbon resins, as well as modified or hydrogenated derivatives.
  • resins which can be used in the context of the invention are polyterpene resins, phenolic or aromatic modified polyterpene resins, modified natural resins such as resin acids from balsam resin, tall resin or root resin, possibly also hydroabietyl alcohol and its esters, acrylic acid copolymers such as styrene-acrylic acid copolymers and resins based on functional Hydrocarbon resins.
  • resins have a low molecular weight of below 2000 g / mol, in particular below 1500 g / mol. They can be chemically inert or they can optionally also contain functional groups, such as OH groups, carboxyl groups or double bonds.
  • soft resins are to be selected that have a dropping temperature below 50.degree , especially below 35 ° C (Mettler dropping point according to ASTM D-3104). Resins which have a softening point between 70 and 130 ° C. (ring-ball method, DIN 52011) can also be added as additional resins. It is preferred to use rosins and in particular fully or partially hydrogenated hydrocarbon resins.
  • the amount of resins that are solid at room temperature can be up to 50% of the total amount of resin.
  • Plasticizers are preferably used to adjust the viscosity or the flexibility and are generally contained in a concentration of 0-25% by weight, preferably 2-15% by weight.
  • Suitable non-polar plasticizers include synthetic oils, paraffinic oils, naphthenic oils or polyisobutylenes. These are, for example, medicinal white oils, naphthenic mineral oils, polypropylene, polybutene, polyisoprene oligomers, hydrogenated polyisoprene and / or polybutadiene oligomers, paraffinic hydrocarbon oils.
  • the sum of soft resin and plasticizer is from 10 to 35% by weight.
  • the hotmelt pressure-sensitive adhesive according to the invention contains additives which can influence certain properties of the adhesive, such as e.g. B. cohesive strength, viscosity, softening point or processing viscosity. These include, for example, stabilizers, waxes, adhesion promoters, antioxidants, light stabilizers, color pigments, rheological agents or similar additives. The amount should be up to 15% by weight. Several additives can also be used as a mixture. Furthermore, fillers can be used to increase strength. To adjust the properties, small amounts of plasticizers such as glycerol, benzoate or phthalate esters or polyglycol ethers can also be added.
  • plasticizers such as glycerol, benzoate or phthalate esters or polyglycol ethers can also be added.
  • waxes can be added to the pressure-sensitive hot-melt adhesive in amounts of from 0 to 5% by weight. The amount is measured in such a way that on the one hand the viscosity is adjusted, but on the other hand the adhesion is not adversely affected.
  • the wax can be of natural or synthetic origin. Vegetable waxes, animal waxes can be used as natural waxes, mineral waxes or petrochemical waxes can be used as synthetic waxes. Preferably, however, waxes should not be included.
  • antioxidants Another group of additives are stabilizers. Their task is to protect the polymers from decomposition during processing.
  • the antioxidants should be mentioned here in particular. They are usually added to the hotmelt pressure-sensitive adhesive in amounts of up to 3% by weight, preferably in amounts of about 0.1 to 1.0% by weight. Such additives are known in principle to the person skilled in the art. He can make a selection based on the desired properties of the hot melt adhesive.
  • the hot-melt pressure sensitive adhesive according to the invention can contain adhesion promoters.
  • Adhesion promoters are substances that improve the adhesion of the hot melt adhesive to the substrate to be bonded.
  • adhesion promoters should improve the aging behavior of bonds under the influence of a humid atmosphere.
  • Typical adhesion promoters are, for example, ethylene / acrylamide comonomers, polymeric isocyanates, reactive organosilicon compounds or phosphorus derivatives.
  • the wetting properties of the adhesive and thus the adhesion to the substrates can also be influenced.
  • a preferred embodiment of the hot melt pressure sensitive adhesive contains 15 to 30 wt. -% of at least one styrene block copolymer, 5 to 35% by weight of at least one tackifying resin which is liquid below 50 ° C, 0 to 25% by weight of a non-polar one Plasticizer and 0 to 15% by weight of other additives, with the sum of the percentages being 100%.
  • the hot-melt pressure-sensitive adhesive according to the invention is produced by known methods by mixing in the melt. All components can be initially introduced, heated and then homogenized, or the components that melt more easily are initially introduced and mixed, then the other resin components are added. It is also possible to produce the hot melt adhesive continuously in an extruder.
  • the suitable hotmelt adhesive is solid and, apart from impurities, free of solvents.
  • the hot melt adhesive suitable according to the invention should have a viscosity of 3000 to 50,000 mPas, preferably 5000 to 30,000, in particular more than 10,000 mPas measured at application temperature. This is 150 ° C (Brookfield, EN ISO 2555, measured at the specified temperature).
  • the hot-melt pressure sensitive adhesives according to the invention are suitable for joining a wide variety of materials.
  • materials such as polyolefin films, for example polyethylene films or polypropylene films, polyolefin webs, for example polyethylene webs or polypropylene webs, polyurethane films, polyurethane foams, films made of cellulose derivatives, films made of polyacrylates or polymethacrylates, films made of polyester, in particular polylactide, polycaprolactone, polyester amide can be connected to one another.
  • the melted adhesive is applied to a substrate and then bonded to a second substrate.
  • the adhesives according to the invention as an adhesive layer to a carrier.
  • the carriers are the known flexible foils, which are also suitable as adhesive tape. These non-tacky films are coated on one or both surfaces with a hot melt adhesive according to the invention.
  • the layer thickness of the applied adhesive is for example from 50 to 500 g / m2 (approx. 50 to 500 ⁇ m). In particular, the layer thickness should be from 100 to 350 g / m2.
  • Such carrier films usually have a non-stick coated back side which can easily be separated from the pressure-sensitive adhesive layer.
  • a special form of use of the hot melt adhesives according to the invention is the coating of self-adhesive films, tapes or labels with an adhesive layer.
  • Tapes or foils for example based on polyolefins or polyesters, are coated with the hot melt adhesive suitable according to the invention.
  • a permanently pressure-sensitive adhesive layer is obtained by selecting an appropriate adhesive. These materials can then be assembled. In this way, permanently sticky foils, labels and tapes can then be produced.
  • the self-adhesive surfaces obtained in this way can optionally be covered by anti-adhesive coated materials.
  • the adhesives of the invention are cloudy. At room temperature a layer 1 cm thick is opaque. However, there is no floating of individual components, so that the adhesive strength of the non-bonded layer or substrates to be bonded is not reduced. Adhesives according to the invention are stable in the melt; there is no phase separation even after prolonged storage in the molten state. The adhesives used according to the invention show good tack. The layers are elastic and show good cohesive cohesion. The two block copolymers form a stable mixture that does not lead to phase separation. A high level of adhesion is obtained.
  • the adhesives according to the invention are known as coatings for film applications.
  • Corresponding coated products can be used in many areas of application, for example as adhesive tapes or Labels, multilayer films for use as security locks, for packaging, in hygiene products or in medical applications.
  • Ethylene / octene copolymer (Infuse D 9808) OBC 5 parts SBS (Kraton D 1118) styrene block copolymer 5 parts SIS (Kraton D 1126) styrene block copolymer 30 parts resin (Escorez 5320) 10 parts Soft resin, (Sylvatac RE12) liquid resin 20 parts naphthenic oil (Nyflex 222B) 1 parts stabilizer (Irganox B 225) Antioxidants Viscosity: 27500 mPas, 150 ° C Viscosity: 15300 mPas, 170 ° C The adhesive is solid or melted in a thin layer cloudy (visual assessment).
  • a carrier film (PE, 50 ⁇ m) is coated with approx. 250 g. After cooling, a film is stuck to a glass plate, pressed on with a roller (1 kg) and stored at 25 ° C. for 24 hours. The bond strength is then measured in a specified time. 20 min 50 N / 25 mm 24 hours 60 N / 25mm 3 d 60 N / 25 mm
  • the adhesion remains constant even after storage, there is no exudation of the incompatible components.
  • Ethylene / octene copolymer (Infuse D 9808) OBC 8 parts SBS (Kraton D 1118) styrene block copolymer 8 parts SIS (Kraton D 1126) styrene block copolymer 43.5 parts resin (Regalite R 1125) 20 parts Polyisobutylenes (Parapol 1300) 0.5 parts stabilizer (Irganox B 225) Antioxidants
  • Viscosity 51200 mPas, 170 ° C
  • the adhesive is solid or melted in a thin layer cloudy (visual assessment).
  • the bond strength of a coated film is low (measured as loop tack, ASTM D6195).
  • Ethylene / octene copolymer (Infuse D 9808) OBC 5 parts SBS (Kraton D 1118) styrene block copolymer 5 parts SIS (Kraton D 1126) styrene block copolymer 40 parts resin (Escorez 5320) 10 parts resin (Foral 85) 10 parts naphthenic oil (Nyflex 222B) 0.5 parts stabilizer (Irganox B 225) Antioxidants
  • Viscosity 42700 mPas, 150 ° C
  • Viscosity 19200 mPas, 170 ° C
  • the bond strength of a coated film (loop tack) is low.

Description

Die Erfindung betrifft Schmelzklebstoffe hergestellt auf Basis von Olefinblockcopolymeren und Styrolblockcopolymeren, die zusammen mit weiteren Zusatzstoffen als Haftschmelzklebstoff geeignet sind.The invention relates to hot-melt adhesives produced on the basis of olefin block copolymers and styrene block copolymers which, together with other additives, are suitable as pressure-sensitive hot-melt adhesives.

Schmelzklebstoffe, die zum Verkleben von verschiedensten Materialien geeignet sind, sind allgemein bekannt. In der EP 0912646 werden Schmelzklebstoffe beschrieben, die aus einem im wesentlichen lineares Copolymer aus Ethylen zusammen mit mindestens einem C3 bis C20-α-Olefinmonomeren hergestellt werden. Auch in der WO 00/00565 werden Schmelzklebstoffe, die auf Basis von linearen Ethylen-α-Olefin-Copolymeren hergestellt werden. Es werden dort die üblichen Zusatzkomponenten beschrieben, z.B. klebrigmachende Harze, Wachse, weitere unterschiedliche Polymere, Styrolblockcopolymere, Weichmacher oder andere Additive. Als Verwendungszweck wird das Verkleben von Papier und Pappmaterialien beschrieben sowie eine Verwendung als Klebeband oder zum Buchbinden. Olefinische Blockcopolymere werden nicht beschrieben.Hot melt adhesives that are suitable for bonding a wide variety of materials are generally known. In the EP 0912646 describes hot melt adhesives which are produced from an essentially linear copolymer of ethylene together with at least one C 3 to C 20 α-olefin monomer. Also in the WO 00/00565 hot melt adhesives are manufactured based on linear ethylene-α-olefin copolymers. The usual additional components are described there, for example tackifying resins, waxes, other different polymers, styrene block copolymers, plasticizers or other additives. The purpose of use is the gluing of paper and cardboard materials, as well as use as adhesive tape or for bookbinding. Olefinic block copolymers are not described.

In der WO 2006/102150 werden Klebstoffe auf Basis ausgewählter C2- α-Olefin Copolymeren beschrieben. Diese Copolymere und ihre Herstellung werden beispielsweise auch in der WO 2005/090426 beschrieben. Dabei werden spezielle Katalysatoren bzw. Überträgerverbindungen erwähnt. Es werden neben anderen Produkten auch Klebstoffe beschrieben. Dabei ist aber festzustellen, dass die Zusammensetzung der Bestandteile der Klebstoffe, ihre Eigenschaften und ihre speziellen Anwendungen nur in Form von Listen, Aufzählungen und aufgabenhaft aufgeführt werden. Eine klare Offenbarung von besonderen Klebstoffzusammensetzungen ist nicht gegeben. Es werden verschiedene allgemeine Eigenschaften beschrieben, insbesondere die Viskosität.In the WO 2006/102150 describes adhesives based on selected C 2 - α-olefin copolymers. These copolymers and their production are, for example, also in the WO 2005/090426 described. Special catalysts or carrier compounds are mentioned here. In addition to other products, adhesives are also described. It should be noted, however, that the composition of the components of the adhesives, their properties and their special uses are only given in the form of lists, enumerations and tasks. There is no clear disclosure of particular adhesive compositions. Various general properties are described, in particular viscosity.

In der WO 2005/028584 werden Schmelzklebstoffe beschrieben, enthaltend Polyolefinpolymere hergestellt über Metallocene-Katalyse. Diese Polymere sollen eine Viskosität bis zu 9000 mPas aufweisen bei einer Temperatur von 149°C, der Schmelzklebstoff selbst eine Viskosität unterhalb 2000 mPas.In the WO 2005/028584 describes hot melt adhesives containing polyolefin polymers produced by metallocenes catalysis. These polymers are said to have a viscosity of up to 9000 mPas at a temperature of 149 ° C, the hot melt adhesive itself has a viscosity below 2000 mPas.

In der US 2008/0281037 werden Polymer und Schmelzklebstoffe beschrieben, unter anderem auch über metallocene-Katalyse hergestellte Olefinblockcopolymere. Es werden keine Gemische mit Styrolblockcopolymeren beschrieben.In the US 2008/0281037 describes polymers and hot-melt adhesives, including olefin block copolymers produced via metallocenes catalysis. No mixtures with styrene block copolymers are described.

WO 2011/022523 A2 offenbart einen Heißschmelzklebstoff mit niedriger Auftragstemperatur, basierend auf Olefincopolymere. US 7199180 B1 offenbart Klebstoffe und Verfahren zu deren Herstellung, umfassend mindestens ein erstes homogenes Ethylene/α-olefin-Interpolymer und gegebenenfalls, Klebrigmacher und Weichmacher. JP 2009185122 A offenbart Propylenharz-Zusammensetzungen, die ausgezeichnete mechanishe Festigkeiteigenschaften und Formbarkeit aufweisen. WO 2011/022523 A2 discloses a low application temperature hot melt adhesive based on olefin copolymers. US 7199180 B1 discloses adhesives and processes for their preparation comprising at least a first homogeneous ethylene / α-olefin interpolymer and optionally, tackifiers and plasticizers. JP 2009185122 A discloses propylene resin compositions excellent in mechanical strength properties and moldability.

Aus den bekannten Olefincopolymeren können Schmelzklebstoffe hergestellt werden. Dabei können die Olefincopolymere in weiten Grenzen variiert werden. Styrolblockcopolymere sind ebenfalls kommerziell weit verfügbar. Sie können in einem weiten Eigenschaftsspektrum hergestellt werden, insbesondere sind es elastische Polymere. Es hat sich jedoch gezeigt, dass Olefincopolymere nicht ausreichend mit Styrolblockcopolymeren verträglich sind. Das führt in der Praxis dazu, dass Klebstoffe aus solchen Gemischen nicht lagerstabil sind oder bei Applikation in der Schmelze. Dabei können sich die Polymere teilweise entmischen, dann sind diese nicht applizierbar, oder an die Oberfläche migrieren und so die Haftung auf den Substraten nachträglich verringern. Das führt dazu, dass solche Mischungen nicht als permanent klebriger Haftschmelzklebstoff geeignet sind. Außerdem ist sicherzustellen, dass eine gute permanente Haftklebrigkeit besteht. Dabei ergeben einige Styrolblockcopolymere nicht klebrige Oberflächen. Wird die Klebrigkeit beispielsweise durch Weichmacher erhöht, wird die Kohäsion reduziert, sodass eine Klebstoffschicht reißt und die Verklebung versagt.Hot-melt adhesives can be produced from the known olefin copolymers. The olefin copolymers can be varied within wide limits. Styrene block copolymers are also widely available commercially. They can be produced with a wide range of properties, especially elastic polymers. However, it has been found that olefin copolymers are not sufficiently compatible with styrene block copolymers. In practice, this means that adhesives made from such mixtures are not storage-stable or when applied in the melt. The polymers can partially separate, in which case they cannot be applied or migrate to the surface and thus subsequently reduce the adhesion to the substrates. As a result, such mixtures are not suitable as permanently tacky pressure-sensitive hot melt adhesives. It must also be ensured that there is good permanent adhesive strength. Some styrene block copolymers result in non-sticky surfaces. If the tackiness is increased, for example by plasticizers, the cohesion is reduced, so that an adhesive layer tears and the bond fails.

Aufgabe der vorliegenden Erfindung ist es deswegen Schmelzklebstoffe zur Verfügung zu stellen, die aus einer Mischung von Olefinblockcopolymeren und Styrolblockcopolymeren bestehen. Die Schmelzklebstoffe sollen eine geeignete Viskosität zeigen, um eine Applikation in dünner Schicht und auf temperaturempfindlichen Substraten zu ermöglichen. Die erhaltenen Schichten sollen haftklebrige Eigenschaften zeigen, die durch Lagerung des Klebstoffs nicht beeinträchtigt werden. Dabei sollen die Klebstoffschichten ein gutes elastisches Verhalten in der Verklebung zeigen.The object of the present invention is therefore to provide hot-melt adhesives which consist of a mixture of olefin block copolymers and styrene block copolymers. The hotmelt adhesives should have a suitable viscosity to enable application in thin layers and on temperature-sensitive substrates. The layers obtained should show pressure-sensitively adhesive properties which are not impaired by storage of the adhesive. The adhesive layers should show good elastic behavior in the bond.

Die Aufgabe wird gelöst durch einen Schmelzklebstoff enthaltend (i) 15 bis 70 Gew.-% eines Gemisches aus mindestens einem Copolymeren auf Basis von Ethylen und/oder Propylen und mindestens einem C4 bis C20-α-Olefin, das durch Metallocene-katalysierte Polymerisation als Blockcopolymer erhältlich ist und mindestens einem Styrolblockcopolymeren, (ii) - 10 bis 70 Gew.-% mindestens eines klebrigmachenden Harzes, (iii) 0 bis 40 Gew.-% weitere Additive und Weichmacher, wobei die Summe der %- Anteile 100% ergeben soll und das klebrigmachende Harz ganz oder teilweise ein Weichharz ist, das bei einer Temperatur unter 50°C flüssig ist.The object is achieved by a hot melt adhesive containing (i) 15 to 70% by weight of a mixture of at least one copolymer based on ethylene and / or propylene and at least one C4 to C20 α-olefin, which is polymerized by metallocenes as Block copolymer is obtainable and at least one styrene block copolymer, (ii) -10 to 70% by weight of at least one tackifying resin, (iii) 0 to 40% by weight of further additives and plasticizers, the sum of the percentages should be 100% and the tackifying resin is wholly or partly a soft resin which is liquid at a temperature below 50 ° C.

Ein weiterer Gegenstand der Erfindung ist die Verwendung solcher Schmelzklebstoffen zum Beschichten von Folien, Bändern, Etiketten und anderen flachen Substarten zum Erzeugen einer haftklebrigen Schicht. Ein weiterer Gegenstand der Erfindung sind Folien, Klebebänder und Etiketten, die auf mindestens einer Seite eine haftklebrige Schicht aus einem erfindungsgemäßen Klebstoff aufweisen.The invention also relates to the use of such hot-melt adhesives for coating films, tapes, labels and other flat substrates to produce a pressure-sensitive adhesive layer. The invention furthermore relates to films, adhesive tapes and labels which have a pressure-sensitive adhesive layer of an adhesive according to the invention on at least one side.

Ein notwendiger Bestandteil des erfindungsgemäßen Haftschmelzklebstoffs sind Olefin-Copolymeren auf Basis von Ethylen und/oder Propylen und mindestens einem C4 bis C20-α-Olefinen. Diese Polyolefine werden über Metallocen-Katalyse hergestellt. Eine Ausführungsform der Erfindung verwendet solche Co- oder Terpolymere auf Basis von Ethylen zusammen C4 bis C20 -α-Olefinen. Bei den Monomeren, die zusätzlich zu Ethylen oder Propylen eingesetzt werden können, handelt es sich um die bekannten mit Ethylen oder Propylen copolymerisierbaren olefinisch ungesättigte Monomere. Insbesondere handelt es sich um lineare oder verzweigte C4 bis C20 -α-Olefine, wie Buten, Hexen, Methylpenten, Octen; cyclisch ungesättigte Verbindungen wie Norbonen oder Norbonadien; symmetrisch oder unsymmetrisch substituierte Ethylen-Derivate, wobei als Substituenten C1 bis C12 -Alkylreste geeignet sind; sowie ggf. ungesättigte Carbonsäuren oder Carbonsäureanhydride. Es kann sich dabei um Homopolymere, Copolymere, Terpolymere handeln, die auch weitere Monomere enthalten können. Im folgenden sollen unter Copolymere auch solche Polymere aus mehr als 2 Monomeren verstanden werden. Dabei soll bevorzugt die Menge der α-Olefin- Comonomere unterhalb 20 % betragen.A necessary component of the hot-melt pressure sensitive adhesive according to the invention are olefin copolymers based on ethylene and / or propylene and at least one C4 to C20 α-olefin. These polyolefins are produced using metallocene catalysis. One embodiment of the invention uses such copolymers or terpolymers based on ethylene together with C4 to C20 α-olefins. For the monomers that can be used in addition to ethylene or propylene, they are the known olefinically unsaturated monomers which can be copolymerized with ethylene or propylene. In particular, they are linear or branched C4 to C20 α-olefins, such as butene, hexene, methylpentene, octene; cyclically unsaturated compounds such as norbonene or norbonadiene; symmetrically or asymmetrically substituted ethylene derivatives, C1 to C12 alkyl radicals being suitable as substituents; and optionally unsaturated carboxylic acids or carboxylic acid anhydrides. These can be homopolymers, copolymers, terpolymers, which can also contain further monomers. In the following, copolymers are also to be understood as meaning polymers composed of more than 2 monomers. The amount of the α-olefin comonomers should preferably be below 20%.

Eine andere Ausführungsform enthält Copolymere auf Basis von Ethylen und Propylen. Gegebenenfalls ist es möglich, dass auch zusätzliche geringe Anteile an C4 bis C20 -α-Olefinen enthalten sind. Diese werden ebenso über Metallocene-Katalysatoren hergestellt. Dabei soll die Menge des Propylen über 60 Gew.-% betragen, insbesondere liegt der Anteil an Propylen über 70 Gew.-%. Es können gegebenen falls noch geringe Anteile an anderen α-Olefinmonomeren enthalten sein, die Menge soll weniger als 5 % betragen, insbesondere sind jedoch Ethylen/Propylen-Blockcopolymere geeignet.Another embodiment contains copolymers based on ethylene and propylene. If necessary, it is possible that additional small proportions of C4 to C20 -α-olefins are also included. These are also produced using metallocenes catalysts. The amount of propylene should be more than 60% by weight, in particular the proportion of propylene is more than 70% by weight. If necessary, small proportions of other α-olefin monomers may also be present, the amount should be less than 5%, but ethylene / propylene block copolymers are particularly suitable.

Die so erhaltenen (Co)polymere weisen ein Molekulargewicht von 2000 bis zu 250000 g/mol auf, insbesondere von 5000 bis zu 100000 g/mol (Molekulargewicht als Zahlenmittel, MN, bestimmt über GPC). Diese (Co)polymere zeichnen sich dadurch aus, dass sie eine enge Molekulargewichtsverteilung aufweisen. Die Molekulargewichtsverteilung ausgedrückt als MW/MN soll beispielsweise bis 2,5 betragen, insbesondere unter 2,3. Solche Polymere sind in der Literatur bekannt und können von verschiedenen Herstellern kommerziell erhalten werden. Beispielsweise sind geeignete Polymere unter dem Handelsnamen Vistamax ® oder Infuse ® kommerziell erhältlich.The (co) polymers obtained in this way have a molecular weight of 2,000 to 250,000 g / mol, in particular from 5,000 to 100,000 g / mol (molecular weight as number average, M N , determined via GPC). These (co) polymers are distinguished by the fact that they have a narrow molecular weight distribution. The molecular weight distribution, expressed as M W / M N, should be, for example, up to 2.5, in particular below 2.3. Such polymers are known in the literature and can be obtained commercially from various manufacturers. For example, suitable polymers are commercially available under the trade name Vistamax® or Infuse®.

Es handelt sich bei den erfindungsgemäß geeigneten Copolymeren um Blockcopolymere. Dabei weisen die Blöcke eine unterschiedliche Zusammensetzung der Monomeren auf. In einer Ausführungsform weisen die erfindungsgemäß geeigneten Schmelzklebstoffe eine Glasübergangstemperatur auf, in einer anderen Ausführungsform sollen die Copolymere zwei Glasübergangstemperaturen aufweisen. Die erste Glasübergangstemperatur (Tg) (gemessen über DTA) soll im Bereich zwischen -100 bis 0°C liegen, insbesondere zwischen -80 bis -10°C. Die zweite Glastemperatur soll insbesondere unterhalb von -100°C liegen.The copolymers suitable according to the invention are block copolymers. The blocks have a different composition of the monomers. In one embodiment, the hot melt adhesives suitable according to the invention have one glass transition temperature, in another embodiment the copolymers should have two glass transition temperatures. The first glass transition temperature (Tg) (measured via DTA) should be in the range between -100 to 0 ° C, in particular between -80 to -10 ° C. The second glass transition temperature should in particular be below -100 ° C.

Insbesondere sind solche olefinischen Blockcopolymere geeignet, die durch Katalyse mit Metallocen-Verbindungen hergestellt werden. Der Schmelzindex dieser Polymere soll von 5 g/10 min bis 200 g/10 min betragen, bevorzugt bis 100 g/10 min (gemessen bei 190 °C, 2,16 kg, DIN ISO 1133). Der Erweichungspunkt der Polymere soll oberhalb von 130°C liegen, insbesondere oberhalb von 160°C. Die Menge dieser Copolymere soll 5 bis 50 Gew.-% bezogen auf dem Schmelzklebstoff betragen, insbesondere zwischen 15 bis 30 Gew.-%. Bei den (Co)polymer kann es sich um ein Polymer handeln, es ist jedoch auch möglich, dass ein Gemisch eingesetzt wird.Those olefinic block copolymers which are prepared by catalysis with metallocene compounds are particularly suitable. The melt index of these polymers should be from 5 g / 10 min to 200 g / 10 min, preferably up to 100 g / 10 min (measured at 190 ° C., 2.16 kg, DIN ISO 1133). The softening point of the polymers should be above 130.degree. C., in particular above 160.degree. The amount of these copolymers should be 5 to 50% by weight based on the hot melt adhesive, in particular between 15 to 30% by weight. The (co) polymers can be a polymer, but it is also possible that a mixture is used.

Als weiteren Bestandteil muss ein erfindungsgemäßer Haftschmelzklebstoff (PSA) mindestens ein thermoplastisches elastisches Styrolblockcopolymer enthalten. Es handelt sich dabei bevorzugt um Triblockcopolymere, es können aber auch Diblockcopolymere eingesetzt werden oder auch Mischungen beider Typen. Solche Blockcopolymere sind schlecht verträglich mit den Olefinblockcopolymeren.As a further component, a hot melt pressure sensitive adhesive (PSA) according to the invention must contain at least one thermoplastic elastic styrene block copolymer. These are preferably triblock copolymers, but diblock copolymers can also be used, or mixtures of both types. Such block copolymers are poorly compatible with the olefin block copolymers.

Es kann sich um verschieden Typen von Styrolblockcopolymeren handeln. Beispiele dafür sind Styrol-Isopren-Blockcopolymere (SIS), Styrol-Isopren-Butadien-Blockcopolymere (SIBS), Styrol-Butadien-Blockcopolymere (SBS), hydrierte Formen der Copolymere, wie SBBS, SEBS, SEPS, SIPS oder deren Mischungen, sowie entsprechende Diblockcopolymere. Solche Polymere sind dem Fachmann bekannt und kommerziell erhältlich. Sie weisen ein Molekulargewicht (MN) von 10000 bis 500000 g/mol auf, insbesondere 70000 bis 300000g/mol. Insbesondere sind nicht hydrierte Formen bevorzugt.There can be different types of styrene block copolymers. Examples of these are styrene-isoprene block copolymers (SIS), styrene-isoprene-butadiene block copolymers (SIBS), styrene-butadiene block copolymers (SBS), hydrogenated forms of the copolymers such as SBBS, SEBS, SEPS, SIPS or their mixtures, as well corresponding diblock copolymers. Such polymers are known to the person skilled in the art and are commercially available. They have a molecular weight (M N ) from 10,000 to 500,000 g / mol, in particular 70,000 to 300,000 g / mol. In particular, non-hydrogenated forms are preferred.

Die Menge der zusätzlich zu den Olefinblockcopolymeren enthaltenen Styrolblockcopolymeren beträgt von 3 bis 35 Gew.%, insbesondere von 5 bis 25 Gew.-%, bezogen auf den Schmelzklebstoff. Durch die Menge dieser Blockcopolymeren wird die Elastizität des Klebstoffs beeinflusst. Sind die Mengen der Blockcopolymeren zu hoch, ist der Klebstoff zu elastisch und kann schlecht verarbeitet werden. Außerdem werden verstärkt Unverträglichkeiten beobachtet, die zu schlechten Klebstoffeigenschaften führen. Ist die Menge zu gering, wird die Kohäsion einer Klebstoffschicht vermindert.The amount of styrene block copolymers contained in addition to the olefin block copolymers is from 3 to 35% by weight, in particular from 5 to 25% by weight, based on the hot-melt adhesive. The elasticity of the adhesive is influenced by the amount of these block copolymers. If the amounts of block copolymers are too high, the adhesive is too elastic and difficult to process. In addition, incompatibilities are increasingly observed, which lead to poor adhesive properties. If the amount is too small, the cohesion of an adhesive layer is decreased.

Als weiteren Bestandteil enthält der erfindungsgemäße Haftschmelzklebstoff mindestens ein klebrigmachendes Harz. Das Harz bewirkt eine zusätzliche Klebrigkeit des Klebstoffs. Es wird in einer Menge von 10 bis 70 Gew.-%, bevorzugt 10 bis 40 Gew.-%, eingesetzt. Erfindungsgemäß ist es notwendig, dass die Harze mindestens anteilig ein Weichharz enthalten, das unter 50°C flüssig oder fließfähig ist. Das kann über die Tropftemperatur bestimmt werden. Harze können dabei ausgewählt werden aus aromatischen, aliphatischen oder cycloaliphatischen Kohlenwasserstoff-Harzen, sowie modifizierte oder hydrierte Derivate. Weitere im Rahmen der Erfindung einsetzbaren Harze sind Polyterpenharze, phenolisch oder aromatisch modifizierte Polyterpenharze, modifizierte Naturharze wie Harzsäuren aus Balsamharz, Tallharz oder Wurzelharz, ggf. auch Hydroabietylalkohol und dessen Ester, Acrylsäure-Copolymerisate, wie Styrol-Acrylsäure-Copolymere und Harze auf Basis funktioneller Kohlenwasserstoffharze.The hot-melt pressure-sensitive adhesive according to the invention contains at least one tackifying resin as a further component. The resin gives the adhesive additional tack. It is used in an amount of 10 to 70% by weight, preferably 10 to 40% by weight. According to the invention, it is necessary that the resins contain at least a proportion of a soft resin that is liquid or flowable below 50 ° C. This can be determined via the drop temperature. Resins can be selected from aromatic, aliphatic or cycloaliphatic hydrocarbon resins, as well as modified or hydrogenated derivatives. Further resins which can be used in the context of the invention are polyterpene resins, phenolic or aromatic modified polyterpene resins, modified natural resins such as resin acids from balsam resin, tall resin or root resin, possibly also hydroabietyl alcohol and its esters, acrylic acid copolymers such as styrene-acrylic acid copolymers and resins based on functional Hydrocarbon resins.

Übliche Harze besitzen ein niedriges Molekulargewicht von unterhalb 2000 g/mol, insbesondere unterhalb von 1500 g/mol. Sie können chemisch inert sein oder sie können gegebenenfalls noch funktionelle Gruppen enthalten, wie beispielsweise OH-Gruppen, Carboxylgruppen oder Doppelbindungen. Erfindungsgemäß sollen dabei Weichharze ausgewählt werden, die eine Tropftemperatur unter 50°C aufweisen, insbesondere unter 35°C (Mettler-Tropfpunkt nach ASTM D-3104). Als zusätzliche Harze können dabei auch solche Harze zugesetzt werden, die einen Erweichungspunkt zwischen 70 und 130°C (Ring-Ball-Methode, DIN 52011) besitzen. Bevorzugt ist es Kolophoniumharze und insbesondere voll- oder teilhydrierte Kohlenwasserstoffharze einzusetzen. Dabei kann die Menge der bei Raumtemperatur festen Harze bis zu 50% der gesamten Harzmenge betragen.Conventional resins have a low molecular weight of below 2000 g / mol, in particular below 1500 g / mol. They can be chemically inert or they can optionally also contain functional groups, such as OH groups, carboxyl groups or double bonds. According to the invention, soft resins are to be selected that have a dropping temperature below 50.degree , especially below 35 ° C (Mettler dropping point according to ASTM D-3104). Resins which have a softening point between 70 and 130 ° C. (ring-ball method, DIN 52011) can also be added as additional resins. It is preferred to use rosins and in particular fully or partially hydrogenated hydrocarbon resins. The amount of resins that are solid at room temperature can be up to 50% of the total amount of resin.

Weichmacher werden vorzugsweise zum Einstellen der Viskosität oder der Flexibilität verwendet und sind im allgemeinen in einer Konzentration von 0 - 25 Gew.%, vorzugsweise von 2 - 15 Gew.% enthalten. Geeignete unpolare Weichmacher umfassen synthetische Öle, paraffinische Öle, naphthenische Öle oder Polyisobutylene. Es handelt sich beispielsweise um medizinische Weißöle, naphtenische Mineralöle, Polypropylen-, Polybuten-, Polyisopren-Oligomere, hydrierte Polyisopren- und/oder Polybutadien-Oligomere, paraffinischen Kohlenwasserstofföle.Plasticizers are preferably used to adjust the viscosity or the flexibility and are generally contained in a concentration of 0-25% by weight, preferably 2-15% by weight. Suitable non-polar plasticizers include synthetic oils, paraffinic oils, naphthenic oils or polyisobutylenes. These are, for example, medicinal white oils, naphthenic mineral oils, polypropylene, polybutene, polyisoprene oligomers, hydrogenated polyisoprene and / or polybutadiene oligomers, paraffinic hydrocarbon oils.

Um einen hohe Klebrigkeit und eine gute Kohäsion zu erhalten ist es bevorzugt, dass die Summe aus Weichharz und Weichmacher von 10 bis 35 Gew.-% beträgt.In order to obtain high tack and good cohesion, it is preferred that the sum of soft resin and plasticizer is from 10 to 35% by weight.

Als weitere Bestandteile sind in dem erfindungsgemäßen Schmelzhaftklebstoff Additive enthalten, die bestimmte Eigenschaften des Klebstoffs beeinflussen können, wie z. B. Kohäsionsfestigkeit, Viskosität, Erweichungspunkt oder Verarbeitungsviskosität. Darunter sind beispielsweise Stabilisatoren, Wachse, Haftvermittler, Antioxidantien, Lichtschutzmittel, Farbpigmente, Rheologiemittel oder ähnliche Zusatzstoffe zu verstehen. Die Menge soll bis zu 15 Gew. % betragen. Es können auch mehrere Additive als Gemisch eingesetzt werden. Weiterhin können Füllstoffe zur Festigkeitserhöhung eingesetzt werden. Zum Einstellen der Eigenschaften können auch noch geringe Mengen an Weichmachern als Glycerin-, Benzoat- oder Phthtalatester oder Polyglykolether zugesetzt werden.The hotmelt pressure-sensitive adhesive according to the invention contains additives which can influence certain properties of the adhesive, such as e.g. B. cohesive strength, viscosity, softening point or processing viscosity. These include, for example, stabilizers, waxes, adhesion promoters, antioxidants, light stabilizers, color pigments, rheological agents or similar additives. The amount should be up to 15% by weight. Several additives can also be used as a mixture. Furthermore, fillers can be used to increase strength. To adjust the properties, small amounts of plasticizers such as glycerol, benzoate or phthalate esters or polyglycol ethers can also be added.

Gegebenenfalls können dem Haftschmelzklebstoff Wachse in Mengen von 0 bis 5 Gew.-% zugegeben werden. Die Menge ist dabei so bemessen, dass einerseits die Viskosität eingestellt wird, andererseits aber die Adhäsion nicht negativ beeinflusst wird. Das Wachs kann natürlichen oder synthetischen Ursprungs sein. Als natürliche Wachse können pflanzliche Wachse, tierische Wachse, als synthetische Wachse können Mineralwachse oder petrochemische Wachse eingesetzt werden. Bevorzugt sollen Wachse aber nicht enthalten sein.If necessary, waxes can be added to the pressure-sensitive hot-melt adhesive in amounts of from 0 to 5% by weight. The amount is measured in such a way that on the one hand the viscosity is adjusted, but on the other hand the adhesion is not adversely affected. The wax can be of natural or synthetic origin. Vegetable waxes, animal waxes can be used as natural waxes, mineral waxes or petrochemical waxes can be used as synthetic waxes. Preferably, however, waxes should not be included.

Eine weitere Gruppe von Additiven sind Stabilisatoren. Sie haben die Aufgabe, die Polymere während der Verarbeitung vor Zersetzung zu schützen. Hier sind insbesondere die Antioxidantien zu nennen. Sie werden üblicherweise in Mengen bis zu 3 Gew.-%, vorzugsweise in Mengen von etwa 0,1 bis 1,0 Gew.-% dem Schmelzhaftklebstoff beigefügt. Solche Additive sind dem Fachmann im Prinzip bekannt. Er kann eine Auswahl nach den erwünschten Eigenschaften des Schmelzklebstoffs treffen.Another group of additives are stabilizers. Their task is to protect the polymers from decomposition during processing. The antioxidants should be mentioned here in particular. They are usually added to the hotmelt pressure-sensitive adhesive in amounts of up to 3% by weight, preferably in amounts of about 0.1 to 1.0% by weight. Such additives are known in principle to the person skilled in the art. He can make a selection based on the desired properties of the hot melt adhesive.

Darüber hinaus kann der erfindungsgemäße Haftschmelzklebstoff Haftvermittler enthalten. Haftvermittler sind Stoffe, die die Adhäsion des Schmelzklebstoffs zu dem zu verklebenden Substrat verbessern. Insbesondere sollen Haftvermittler das Alterungsverhalten von Klebungen unter Einfluss von feuchter Atmosphäre verbessern. Typische Haftvermittler sind zum Beispiel Ethylen/Acrylamid-Comonomere, polymere Isocyanate, reaktive siliciumorganische Verbindungen oder Phosphorderivate. Ebenso können die Benetzungseigenschaften des Klebstoffs und damit das Haftvermögen auf den Substraten beeinflusst werden.In addition, the hot-melt pressure sensitive adhesive according to the invention can contain adhesion promoters. Adhesion promoters are substances that improve the adhesion of the hot melt adhesive to the substrate to be bonded. In particular, adhesion promoters should improve the aging behavior of bonds under the influence of a humid atmosphere. Typical adhesion promoters are, for example, ethylene / acrylamide comonomers, polymeric isocyanates, reactive organosilicon compounds or phosphorus derivatives. The wetting properties of the adhesive and thus the adhesion to the substrates can also be influenced.

Eine bevorzugt Ausführungsform des Haftschmelzklebstoffs enthält 15 bis 30 Gew.-% eines Blockcopolymeren auf Basis von Ethylen und/oder Propylen und gegebenenfalls mindestens einem C4 bis C20-α-Olefinen, das durch Metallocene-katalysierte Polymerisation erhältlich ist, und 5 bis 35 Gew.-% mindestens eines Styrolblockcopolymeren, 5 bis 35 Gew.-% mindestens eines klebrigmachenden Harzes, das unter 50 °C flüssig ist, 0 bis 25 Gew.-% eines unpolaren Weichmachers sowie 0 bis 15 Gew.-% weitere Additive, wobei die Summe der %-Anteile 100% ergeben soll.A preferred embodiment of the hot melt pressure sensitive adhesive contains 15 to 30 wt. -% of at least one styrene block copolymer, 5 to 35% by weight of at least one tackifying resin which is liquid below 50 ° C, 0 to 25% by weight of a non-polar one Plasticizer and 0 to 15% by weight of other additives, with the sum of the percentages being 100%.

Der erfindungsgemäße Haftschmelzklebstoff wird durch bekannte Verfahren durch Mischen in der Schmelze hergestellt. Dabei können alle Komponenten gleichzeitig vorgelegt, erwärmt und dann homogenisiert werden, oder es werden zuerst die leichter schmelzenden Komponenten vorgelegt und gemischt, danach die weiteren Harzbestandteile zugegeben. Es ist auch möglich, den Schmelzklebstoff kontinuierlich in einem Extruder herzustellen. Der geeignete Schmelzklebstoff ist fest und, bis auf Verunreinigungen, frei von Lösemitteln.The hot-melt pressure-sensitive adhesive according to the invention is produced by known methods by mixing in the melt. All components can be initially introduced, heated and then homogenized, or the components that melt more easily are initially introduced and mixed, then the other resin components are added. It is also possible to produce the hot melt adhesive continuously in an extruder. The suitable hotmelt adhesive is solid and, apart from impurities, free of solvents.

Der erfindungsgemäß geeignete Schmelzklebstoff soll eine Viskosität von 3000 bis 50000 mPas aufweisen, bevorzugt von 5000 bis 30000, insbesondere über 10000 mPas gemessen bei Applikationstemperatur. Diese liegt bei 150°C (Brookfield, EN ISO 2555, gemessen bei angegebener Temperatur).The hot melt adhesive suitable according to the invention should have a viscosity of 3000 to 50,000 mPas, preferably 5000 to 30,000, in particular more than 10,000 mPas measured at application temperature. This is 150 ° C (Brookfield, EN ISO 2555, measured at the specified temperature).

Die erfindungsgemäßen Haftschmelzklebstoffe eignen sich zum Verbinden unterschiedlichster Materialien. So lassen sich Materialien wie Polyolefinfolien, beispielsweise Polyethylenfolien oder Polypropylenfolien, Polyolefinvliese, beispielsweise Polyethylenvliese oder Polypropylenvliese, Polyurethanfolien, Polyurethanschäume, Folien aus Cellulosederivaten, Folien aus Polyacrylaten oder Polymethacrylaten, Folien aus Polyester, insbesondere Polylactid, Polycaprolacton, Polyesteramid untereinander verbinden. Dabei werden die aufgeschmolzenen Klebstoff auf ein Substrat aufgetragen und danach mit einem zweiten Substrat verklebt.The hot-melt pressure sensitive adhesives according to the invention are suitable for joining a wide variety of materials. For example, materials such as polyolefin films, for example polyethylene films or polypropylene films, polyolefin webs, for example polyethylene webs or polypropylene webs, polyurethane films, polyurethane foams, films made of cellulose derivatives, films made of polyacrylates or polymethacrylates, films made of polyester, in particular polylactide, polycaprolactone, polyester amide can be connected to one another. The melted adhesive is applied to a substrate and then bonded to a second substrate.

Eine andere bevorzugte Ausführungsform trägt die erfindungsgemäßen Klebstoffe als Klebeschicht auf einen Träger auf. Bei den Trägern handelt es sich um die bekannten flexiblen Folien, die auch als Klebeband geeignet sind. Diese nicht klebrigen Folien werden an einer oder beiden Oberflächen mit einem erfindungsgemäßen Schmelzklebstoff beschichtet. Die Schichtdicke des aufgetragenen Klebstoffs beträgt beispielsweise von 50 bis 500 g/m2 (ca. 50 bis 500 µm). Insbesondere soll die Schichtdicke von 100 bis 350 g/m2 betragen.Another preferred embodiment applies the adhesives according to the invention as an adhesive layer to a carrier. The carriers are the known flexible foils, which are also suitable as adhesive tape. These non-tacky films are coated on one or both surfaces with a hot melt adhesive according to the invention. The layer thickness of the applied adhesive is for example from 50 to 500 g / m2 (approx. 50 to 500 µm). In particular, the layer thickness should be from 100 to 350 g / m2.

Diese Klebstoffschichten weisen eine gute Haftung zu dem Trägermaterial auf. Solche Trägerfolien weisen üblicherweise eine anti-haft beschichtete Rückseite auf, die leicht von der Haftklebstoffschicht getrennt werden kann.These adhesive layers adhere well to the carrier material. Such carrier films usually have a non-stick coated back side which can easily be separated from the pressure-sensitive adhesive layer.

Eine spezielle Verwendungsform der erfindungsgemäßen Schmelzklebstoffe ist die Beschichtung von selbstklebenden Folien, Bändern oder Etiketten mit einer Klebstoffschicht. Dabei werden Bänder oder Folien, beispielsweise auf Basis von Polyolefinen oder Polyestern, mit dem erfindungsgemäß geeigneten Schmelzklebstoff beschichtet. Es wird in diesem Fall durch Auswahl eines entsprechenden Klebstoffs eine dauerhaft haftklebrige Schicht erhalten. Danach können diese Materialien konfektioniert werden. Auf diese Weise können dann dauerklebrige Folien, Etiketten und Bänder hergestellt werden. Die so erhaltenen selbstklebenden Oberflächen können gegebenenfalls durch anti-adhäsiv beschichtete Materialien abgedeckt werden.A special form of use of the hot melt adhesives according to the invention is the coating of self-adhesive films, tapes or labels with an adhesive layer. Tapes or foils, for example based on polyolefins or polyesters, are coated with the hot melt adhesive suitable according to the invention. In this case, a permanently pressure-sensitive adhesive layer is obtained by selecting an appropriate adhesive. These materials can then be assembled. In this way, permanently sticky foils, labels and tapes can then be produced. The self-adhesive surfaces obtained in this way can optionally be covered by anti-adhesive coated materials.

Die erfindungsgemäßen Klebstoffe sind trüb. Bei Raumtemperatur ist eine Schicht von 1 cm Dicke undurchsichtig. Es findet aber kein Ausschwimmen von einzelnen Bestandteilen statt, damit wird auch die Klebekraft der nicht verklebten Schicht oder zu verklebten Substraten nicht vermindert. In der Schmelze sind erfindungsgemäße Klebstoffe stabil, es ergibt sich auch bei längerer Lagerung im geschmolzenen Zustand keine Phasentrennung. Die erfindungsgemäß verwendeten Klebstoffe zeigen eine gute Klebrigkeit. Dabei sind die Schichten elastisch und zeigen einen guten kohäsiven Zusammenhalt. Die beiden Blockcopolymere bilden eine stabile Mischung, die nicht zu einer Phasentrennung führt. Dabei wird eine hohe Adhäsion erhalten.The adhesives of the invention are cloudy. At room temperature a layer 1 cm thick is opaque. However, there is no floating of individual components, so that the adhesive strength of the non-bonded layer or substrates to be bonded is not reduced. Adhesives according to the invention are stable in the melt; there is no phase separation even after prolonged storage in the molten state. The adhesives used according to the invention show good tack. The layers are elastic and show good cohesive cohesion. The two block copolymers form a stable mixture that does not lead to phase separation. A high level of adhesion is obtained.

Die erfindungsgemäßen Klebstoffe sind als Beschichtung für Folienanwendung bekannt. Entsprechende beschichtetet Produkte können in vielen Anwendungsgebieten eingesetzt werden, beispielsweise als Klebebänder oder Etiketten, Mehrschichtfolien zur Anwendung als Verschlusssicherungen, für Verpackungen, in Hygieneprodukte oder in medizinischen Anwendungen.The adhesives according to the invention are known as coatings for film applications. Corresponding coated products can be used in many areas of application, for example as adhesive tapes or Labels, multilayer films for use as security locks, for packaging, in hygiene products or in medical applications.

Beispiele:Examples: Beispiel 1:Example 1:

20 Teile Ethylen/Octen-copolymer (Infuse D 9808) OBC 5 Teile SBS (Kraton D 1118) Styrolblock-Copolymer 5 Teile SIS (Kraton D 1126) Stryrolblockcopolymer 30 Teile Harz (Escorez 5320) 10 Teile Weichharz, (Sylvatac RE12) flüssiges Harz 20 Teile naphthenisches Öl (Nyflex 222B) 1 Teile Stabilisator (Irganox B 225) Antioxidants Viskosität: 27500 mPas, 150°C
Viskosität: 15300 mPas, 170°C
Der Klebstoff ist fest oder geschmolzen in dünner Schicht trüb (visuelle Beurteilung). 20 parts Ethylene / octene copolymer (Infuse D 9808) OBC 5 parts SBS (Kraton D 1118) styrene block copolymer 5 parts SIS (Kraton D 1126) styrene block copolymer 30 parts resin (Escorez 5320) 10 parts Soft resin, (Sylvatac RE12) liquid resin 20 parts naphthenic oil (Nyflex 222B) 1 parts stabilizer (Irganox B 225) Antioxidants Viscosity: 27500 mPas, 150 ° C
Viscosity: 15300 mPas, 170 ° C
The adhesive is solid or melted in a thin layer cloudy (visual assessment).

Ein Trägerfilm (PE, 50µm) wird mit ca. 250 g beschichtet.
Nach dem Abkühlen wird ein Film auf eine Glasplatte geklebt, mit einer Rolle (1kg) angedrückt und 24 Std. bei 25°C gelagert. Danach wird in festgelegter Zeit die Klebkraft gemessen. 20 min 50 N / 25 mm 24 h 60 N / 25mm 3 d 60 N / 25 mm A carrier film (PE, 50 µm) is coated with approx. 250 g.
After cooling, a film is stuck to a glass plate, pressed on with a roller (1 kg) and stored at 25 ° C. for 24 hours. The bond strength is then measured in a specified time. 20 min 50 N / 25 mm 24 hours 60 N / 25mm 3 d 60 N / 25 mm

Die Adhäsion bleibt konstant auch nach Lagerung, es findet kein Ausschwitzen der unverträglichen Komponenten statt.The adhesion remains constant even after storage, there is no exudation of the incompatible components.

Vergleichsbeispiel 2:Comparative example 2:

20 Teile20 parts Ethylen/Octen-copolymerEthylene / octene copolymer (Infuse D 9808) OBC(Infuse D 9808) OBC 8 Teile8 parts SBSSBS (Kraton D 1118) Styrolblock-Copolymer(Kraton D 1118) styrene block copolymer 8 Teile8 parts SISSIS (Kraton D 1126) Stryrolblockcopolymer(Kraton D 1126) styrene block copolymer 43,5 Teile43.5 parts Harzresin (Regalite R 1125)(Regalite R 1125) 20 Teile20 parts PolyisobutylenePolyisobutylenes (Parapol 1300)(Parapol 1300) 0,5 Teile0.5 parts Stabilisatorstabilizer (Irganox B 225) Antioxidants(Irganox B 225) Antioxidants

Viskosität: 51200 mPas, 170°C
Der Klebstoff ist fest oder geschmolzen in dünner Schicht trüb (visuelle Beurteilung).
Die Klebkraft einer beschichteten Folie ist gering (gemessen als loop tack, ASTM D6195).Viscosity: 51200 mPas, 170 ° C
The adhesive is solid or melted in a thin layer cloudy (visual assessment).
The bond strength of a coated film is low (measured as loop tack, ASTM D6195).

Vergleichsbeispiel 3:Comparative example 3:

20 Teile20 parts Ethylen/Octen-copolymerEthylene / octene copolymer (Infuse D 9808) OBC(Infuse D 9808) OBC 5 Teile5 parts SBSSBS (Kraton D 1118) Styrolblock-Copolymer(Kraton D 1118) styrene block copolymer 5 Teile5 parts SISSIS (Kraton D 1126) Stryrolblockcopolymer(Kraton D 1126) styrene block copolymer 40 Teile40 parts Harzresin (Escorez 5320)(Escorez 5320) 10 Teile10 parts Harzresin (Foral 85)(Foral 85) 10 Teile10 parts naphthenisches Ölnaphthenic oil (Nyflex 222B)(Nyflex 222B) 0,5 Teile0.5 parts Stabilisatorstabilizer (Irganox B 225) Antioxidants(Irganox B 225) Antioxidants

Viskosität: 42700 mPas, 150°C
Viskosität: 19200 mPas, 170°C
Die Klebkraft einer beschichteten Folie (loop tack) ist gering.Viscosity: 42700 mPas, 150 ° C
Viscosity: 19200 mPas, 170 ° C
The bond strength of a coated film (loop tack) is low.

Claims (10)

  1. A hot-melt adhesive containing
    - 15 to 70 wt.% of a mixture of at least one copolymer based on ethylene and/or propylene, and at least one C4 to C20 α-olefin which can be obtained as a block copolymer by metallocene-catalyzed polymerization, and at least one styrene block copolymer,
    - 10 to 70 wt.% of at least one tackifying resin,
    - 0 to 40 wt.% of further additives,
    wherein the sum of the percentages should be 100% and the tackifying resin is entirely or in part a soft resin which is liquid at a temperature below 50 °C.
  2. The hot-melt adhesive according to claim 1, characterized in that the tackifying soft resins have a dropping point below 35 °C.
  3. The hot-melt adhesive according to one of claims 1 or 2, characterized in that the styrene block copolymers are selected from non-hydrogenated block copolymers.
  4. The hot-melt adhesive according to one of claims 1 to 3, characterized in that the adhesive is cloudy at room temperature.
  5. The hot-melt adhesive according to one of claims 1 to 4, characterized in that the hot-melt adhesive has a viscosity between 3000 mPas and 50,000 mPas (at 150 °C).
  6. The hot-melt adhesive according to one of claims 1 to 5, characterized in that non-polar plasticizers, in particular synthetic oils, paraffinic oils, naphthenic oils or polyisobutylene oils, are used as plasticizers.
  7. The hot-melt adhesive according to claim 3, characterized in that the styrene block copolymers in particular include SIS, SBS or SIBS.
  8. The hot-melt adhesive according to claim 1, characterized in that 15 to 30 wt.% olefin block copolymers, 5 to 35 wt.% of a styrene block copolymer, 5 to 35 wt.% liquid tackifying resin and 25 to 0 wt.% plasticizer are contained.
  9. The use of hot-melt adhesives according to one of claims 1 to 8 as a pressure-sensitive adhesive.
  10. The use according to claim 11 for coating films, tapes or labels.
EP12790893.7A 2011-11-22 2012-11-22 Psa containing olefin block copolymers and styrene block copolymer Active EP2782969B1 (en)

Applications Claiming Priority (2)

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DE102011086845A DE102011086845A1 (en) 2011-11-22 2011-11-22 PSA containing olefin block copolymers and styrenic block copolymers
PCT/EP2012/073293 WO2013076175A1 (en) 2011-11-22 2012-11-22 Psa containing olefin block copolymers and styrene block copolymer

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MX354708B (en) 2018-03-16
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BR112014012114A8 (en) 2017-06-20
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IN2014CN03686A (en) 2015-07-03
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EP2782969A1 (en) 2014-10-01
US20140256867A1 (en) 2014-09-11
US9732258B2 (en) 2017-08-15
DE102011086845A1 (en) 2013-05-23
KR20140094558A (en) 2014-07-30

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